Process of making dipolymer



Patented Nov. 13, 1928.

UNITED STATES 1,691,573 PATENT OFFICE.

IRVIN W. HUMPHREY, OF WEAR-TON, NEW JERSEY, ASSIGNOR TO HERCULES POW- DER COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE.

PROCESS OF MAKING DIPOLY'MER.

No Drawing.-

The object of my invention is to produce -Dipolymer.

' Dipolymer, as the term is herein employed,

is a product, consisting of polymerized ter- 185 C., which is obtained in the steam distillation of pine wood. Pure dipentene boils at 1746 C., but the term dipentene as herein used is intended to comprehend the crude product with the Wider boiling range.

It is known to make Dipolymer in the liquid phase by treating turpentine or dipentene with sulfuric acid of various concentrations. I have discovered that it may be prepared, by a simple and economical new process, from pine oil, I have discovered that it may be made either in the liquid phase or the vapor phase-in the former case by treatment with fullers earth, or an equivalent polymerizing agent, and in the latter case by a somewhat difierent process in which the use of fullers earth or equivalent polymerizing agent is desirable, but not indispensable, and functions as a catalyst. In the case of pine oil, which consists largely of tertiary terpene alcohols, the fullers earth causes two reactions: (1) dehydration of the pine oil to dipentene and other hydrocarbons, as

' and (2) a polymerization of the hydrocar- 40 bons to the Dipolymer plus a smaller propor tion of the higher polymers, as:

Application filed July 20, 1926. Serial No. 128,812.

tures above 250 C. a depolymerization is noticeable. It is usually of advantage to allow the water formed during the process to distill off during the operation. The earth may be re-used.

For example, 400 parts of pine oilv are heated with 100 parts of fuller s earth in a bath held at 160170 C. for eight hours. After cooling, the product is filtered from the fullers earth and then distilled, 125 parts distilling below 250 C. The residue is Dipolymer. A portion of the lower boiling fraction can be converted into Dipolymer by again treating it with fullers earth, but a large proportion of non-polymerizable hydrocarbons, including para-cymene, is present. The bath may be held at higher temperatures in order to decrease the period of heating. The pine oil may be refluxed with the fullers earth.

Other clays, or silicious or argillaceous earths, such as filtrol, heated oxides, such as aluminum oxide, metallic chlorides, prenerabl anhydrous, such as zinc chloride, stannic c loride, aluminum chloride, and ferric chloride, as well as other polymerizing agents, may be substituted for fullers earth; or mineral earth may be impregnated with an anhydrous metallic chloride or oxide in order to efl'ect polymerization at a lower temperature.

The crude product which is obtained on polymerizing pine oil may be employed, in some instances, Without refining; but it is usually preferably to distill off the lower boilin end, cuttin around 250 C. By this procedure, the hy rocarbons and any unaltered pine oil are separated, leaving a residu consisting of crude Dipolymer,

, Polymerization in the vapor phase may be carried out at temperatures ranging from 200550 O. by passing the vapors of pine oil through a tube of iron or other suitable mate rial at such a rate as will permit the vapors to remain in contact with a catalyst, contained in the tube, long enough to cause a partial polymerization. Heat alone will cause polymerization, but a catalyst, such 88... fullers earth, is desirable. For exam 1e, through an iron tube 28" x 1", heate to around 475 (3., filled with 8-10 mesh fullers earth, is passed 200 cc. of pine oil at a rate of 50 cc. per hour. There were obtained 166 cc. of a product containing 44 cc. of Dipolymer. A portion of the unpolymerize oil was polymerized by re-passing through the tube.

A. typical sample of crude Dipolymer has a specific gravity of 0.95, and the following boilin range: 5% over at 305 C., 20% at 326 50% at 335 C1, 70" at 342 C. and

90% at 375 C. If a cut is made when approximately 80% has distilled over, a prodnot is obtained having a specific gravity of 0.94. A second cut may be made comprising approximately the 80-95% portion of the crude Dipolymer. This cut is exceedingly viscous and resembles a soft rosin. The residue is hard and brittle and has the appearance of a dark colored rosin. For some applications of the Dipolymer it may be desirable to separate it into cuts as outlined above.

I do not herein claim the above described preparation of Dipolymer in the liquid phase, the same forming the subject-matter of a separate application.

Having now fully described my invention, what I claim and desire to protect by Letters Patent is:

1. The process of preparing Dipolymer from pine oil which includes heating ine oil to a temperaturein excess of 200 C. and below a temperature of 550 (31- for a sutficient, length of time to efiect dehydration and finally polymerization of a substantial part of the pine oil vapors to form Dipolymer.

2. The process of preparing Dipolymer from pine oil which includes vaporizing pine oil and passing the vapors in intimate contact with a catalyst for such length of time and at such temperature as will efiect dehydration and- .finally polymerization of a substantial art of the pine oil vapors to form Dipo ymer.

3. The process of preparing Dipolymer from pine oil which includes vaporizing pine oil and passing the vapors through a permeable catalyst for such length of time and at such temperature as will effect dehydration and finally polymerization of a substantial part of the pine oil vapors to form Dipolymer.

4. The process of preparing Dipolymer from pine oil which includes passing the vapors of pine oil, while at a temperature above 200 C. and below 550 0., in intimate contact with a catalyst for\ such length of time as will efi'ect dehydration and finally polymerization of a substantial part of the pine oil vapors to form Dipolymer.

5. The process of preparing Dipolymer from pine oil which includes heating pine oil to a temperature in excess of 200 'C. and below a temperature of 550 C. for a sufiicient length of time to efiect dehydration and finally polymerization of a substantial part of the pine oil vapors, condensing the product, and reheating to a temperature required to vaporize the lower boiling fractions of the same, leaving a residue which comprises principally Dipolymer.

6. The process of preparing Dipolymer from pine oil which includes passing the vapors of pine oil, while at a temperature above 200 C. and below 550 (1, in intimate contact with a cataylst for such length of time as will effect dehydration and finally polymerization of a substantial part of the pine oil vapors, condensing the product, and reheating to a-temperature required to vaporize the lower boiling fractions of the same, leavin a residue which comprises principally Dipolymer.

7. The process of preparin Dipolymer from pine oil which includes eating pine oil to a temperature in excess of 200 C. and below a temperature of 550 C. for a sufiicient length of time to efiect deh dration and finally polymerization of a su stantial part of the pine oil vapors, condensing the product, and fractionally distillin the same at temperatures adapted to yield products having specific gravities progressively lower than f D 1 8. e recess 0 pre arin i 0 er from pine oil which inc udes pass ing lihe vapors of pine oil, while at a temperature above 200 C. and below 550 C., in intimate contact with a catalyst for such length of time as will .efiect dehydration and finally polymerization of a substantial part of the pine oil vapors, condensing the product, and

'oil and passing the vapors in intimate contact with fullers earth for such length of time and at such temperature-as will effect dehydration and finally polymerization of a substantial part of the pine oil vapors to form Dipolymer.

In testimony of which invention, I have hereunto set my hand at Philadelphia, Pennsylvania, on this 2nd day of July, 1926.

IRVIN w. HUMPHREY. 

